US5422422A - High refractive index plastic base on an alkylthiol and an alkylpolythiol ester - Google Patents
High refractive index plastic base on an alkylthiol and an alkylpolythiol ester Download PDFInfo
- Publication number
- US5422422A US5422422A US08/134,736 US13473693A US5422422A US 5422422 A US5422422 A US 5422422A US 13473693 A US13473693 A US 13473693A US 5422422 A US5422422 A US 5422422A
- Authority
- US
- United States
- Prior art keywords
- refractive index
- high refractive
- ester
- alkylpolythiol
- alkylthiol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004033 plastic Substances 0.000 claims abstract description 22
- 229920003023 plastic Polymers 0.000 claims abstract description 22
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 150000001356 alkyl thiols Chemical class 0.000 claims abstract description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- SSDRLRBANNHTFJ-UHFFFAOYSA-N ethane-1,1-dithiol;2-methylprop-2-enoic acid Chemical group CC(S)S.CC(=C)C(O)=O.CC(=C)C(O)=O SSDRLRBANNHTFJ-UHFFFAOYSA-N 0.000 claims description 7
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 6
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 3
- PTCUDMFNJUXQAW-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,1-dithiol Chemical group CCC(S)S.CC(=C)C(O)=O PTCUDMFNJUXQAW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 4
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 9
- WWHPXBHYWHTERP-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,1-dithiol Chemical compound CCC(S)S.CC(=C)C(O)=O.CC(=C)C(O)=O WWHPXBHYWHTERP-UHFFFAOYSA-N 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- -1 aromatic dithiols Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- VSKAJYQVWVOVRT-UHFFFAOYSA-N 2,3-bis[(2-sulfanylacetyl)oxy]propyl 2-sulfanylacetate Chemical compound SCC(=O)OCC(OC(=O)CS)COC(=O)CS VSKAJYQVWVOVRT-UHFFFAOYSA-N 0.000 description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- VLCCKNLIFIJYOQ-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] 2,2,3,3-tetrakis(sulfanyl)propanoate Chemical compound OCC(CO)(CO)COC(=O)C(S)(S)C(S)S VLCCKNLIFIJYOQ-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 229920006295 polythiol Polymers 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 1
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 description 1
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 1
- JQNQFWKIHVWZND-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,3-dithiol Chemical compound SCCCS.CC(=C)C(O)=O.CC(=C)C(O)=O JQNQFWKIHVWZND-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- RXDRVFFZJRNHEG-UHFFFAOYSA-N CC(S)S.CC(=C)C(O)=O Chemical compound CC(S)S.CC(=C)C(O)=O RXDRVFFZJRNHEG-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000006841 cyclic skeleton Chemical group 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920002100 high-refractive-index polymer Polymers 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- NCNISYUOWMIOPI-UHFFFAOYSA-N propane-1,1-dithiol Chemical compound CCC(S)S NCNISYUOWMIOPI-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- FZZVCAVCHWPLOW-UHFFFAOYSA-N s-[2-[1-(2-methylprop-2-enoylsulfanyl)ethylsulfanyl]ethyl] 2-methylprop-2-enethioate Chemical compound CC(=C)C(=O)SC(C)SCCSC(=O)C(C)=C FZZVCAVCHWPLOW-UHFFFAOYSA-N 0.000 description 1
- AGGHKNDQWUYBAS-UHFFFAOYSA-N s-[2-[3-[2-(2-methylprop-2-enoylsulfanyl)ethylsulfanyl]propylsulfanyl]ethyl] 2-methylprop-2-enethioate Chemical compound CC(=C)C(=O)SCCSCCCSCCSC(=O)C(C)=C AGGHKNDQWUYBAS-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/38—Esters containing sulfur
Definitions
- the invention relates to a high refractive index plastic, produced by reacting an alkylpolythiol with an alkylpolythiol ester of (meth)acrylic acid, under the conditions of radical polymerization.
- a high refractive index is very advantageous for plastics which are to be used in optical elements.
- a high refractive index of the material can be achieved, e.g., by incorporating sulfur atoms into the plastic.
- One means of introducing sulfur into a polymer chain, is by thiol addition to an organic isocyanate.
- high refractive index polymers are proposed which are produced from polythiols and polyisocyanates, or from sulfur-containing polyisocyanates and polyisothiocyanates.
- the optical dispersion of such polyurethane derivatives is excessive.
- An exception is the case of polymers with halogen-containing aromatic dithiols.
- the halogen content presents drawbacks in processing and toxicity.
- Thiol-ene addition can also be used to produce optical materials, e.g. in the form of addition products of polythiols to multiply unsaturated compounds.
- An example of this is the use of dimethacrylates of dihydric alcohols (see, e.g., EP-A 437,374 and 284,374).
- the refractive index of such materials is insufficiently high.
- the polymers claimed in EP 394,495 have high indices of refraction (>1.65), but the aromatic diene (4,4,'-bis((meth)acryloylthio)diphenyl sulfide) causes a high dispersion of light.
- the sulfur-containing polymers of the state of the art are not satisfactory for use in optical components, either as to their optical properties or their mechanical properties.
- the underlying problem of the invention is to devise transparent, colorless plastics with a high refractive index and a high Abbe number.
- transparent, colorless polymers with very good optical properties can be produced by reacting polythiols with multifunctional alkyl thio(meth)acrylates under conditions of simultaneous polymerization and polyaddition.
- the invention relates to a high refractive index plastic K produced by reaction of an alkylthiol with a multiply unsaturated monomer, wherein said alkylthiol (A) has at least 2, and up to 20 carbon atoms in the alkyl group, and contains at least 2 thiol groups in the molecule, is reacted with an alkylpolythiol ester (B) having at least 2, and up to 24, preferably up to 12, carbon atoms in the alkyl group, which ester contains at least 2 thiol groups esterified with (meth)acrylic acid in the molecule, said reaction being under conditions of radical polymerization, with the limitation that the numerical ratio of the mercapto groups to the available double bonds is ⁇ 1, preferably ⁇ 0.5.
- the structure of the alkylthiol (A) is preferably such that the density of sulfur atoms per unit volume is high. This can be achieved, e.g., by employing a branched or cyclic skeleton, e.g. neopentyl.
- a branched or cyclic skeleton e.g. neopentyl.
- the thiol groups advantageously one may start with hydroxyl groups on the molecule, which are then, e.g., esterified with thioglycolic acid. In this way, e.g. pentaerythritol may be esterified with thioglycolic acid to form pentaerythritol tetrathioglycolate (compound A-I).
- Cyclic polyols such as, e.g., sugar alcohols may be esterified in a similar fashion.
- the alkylpolythiol ester (B) is represented by the general formula I ##STR1## where R represents hydrogen or methyl; and Y represents a C 2-24 alkyl group, preferably a C 2-12 alkyl group, a C 2-24 branched alkyl group, preferably a C 2-12 branched alkyl group, a C 3-24 cyclic alkyl group, preferably a C 3-12 cyclic alkyl group, said alkyl, branched alkyl or cyclic alkyl optionally containing ether or thioether groups, and optionally being substituted with additional ##STR2## groups.
- R represents hydrogen or methyl
- Y represents a C 2-24 alkyl group, preferably a C 2-12 alkyl group, a C 2-24 branched alkyl group, preferably a C 2-12 branched alkyl group, a C 3-24 cyclic alkyl group, preferably a C 3-12 cyclic alkyl group, said
- subject compounds are ethanedithiol methacrylate bisester, and propanedithiol methacrylate bisester (hereinafter, “ethanedithiol dimethacrylate” and “propanedithiol dimethacrylate”).
- the starting compounds (A) and (B) may be produced by conventional methods which are known to those of ordinary skill in the art.
- Suitable initiators are the known radical initiators, e.g. azo initiators such as azobis(isobutyronitrile) (AIBN), in the usual amounts, e.g. 0.1-1 wt. % (based on the weight of the monomers).
- azo initiators such as azobis(isobutyronitrile) (AIBN)
- AIBN azobis(isobutyronitrile)
- the polymerization may be carried out, e.g., in bulk (i.e. without solvent), wherein it may be between two glass plates, in the manner which is common with polymerization of methyl methacrylate in the mass.
- Solution polymerization e.g. is another possibility.
- the plastic E is comprised of units of the components (A) and (B) and may also contain additives known from acrylate chemistry, such as stabilizers, parting compounds, and possibly colorants (see Gaechter, R., and Mueller, H., 1979, “Taschenbuch der Kunststoff-Additive” pub. Hanser-Verlag)
- a homogeneous mixture of components (A) and (B) and the initiator is prepared and charged into a space between two glass plates.
- Polymerization is initiated by an energy supply; e.g., by energetic radiation, particularly UV light, or by heating, advantageously in a water bath, wherewith the energy is supplied over an extended period, e.g. 24-30 hr.
- the temperature is increased during the polymerization, e.g. over the range 40°-90° C.
- the resulting plastic K is a very clear, colorless, hard plate.
- the plastic K preferably has a refractive index of >1.589 and an Abbe number of >38.6.
- the inventive plastic E is well suited for numerous applications, particularly in the optics area.
- E.g., prisms, lenses, eyeglass lenses, and other optical components may be produced from the plastic K.
- a monomer mixture of 23.8 g ethylene glycol dimethacrylate, 13.0 g pentaerythritol tetrathioglycolate, and 148 mg azobis(isobutyronitrile) was polymerized as in Example 1.
- the polymer obtained was also clear and hard, and had a refractive index of 1.5356 and Abbe number 51.
- the homopolymer was produced by a procedure analogous to that of Examples 1 and 2. A clear but very brittle material was obtained, with a refractive index of 1.6075 and Abbe number 35.
- Example 4 The same procedure as in Example 4 was followed, but with the use of 30.4 g propanedithiol dimethacrylate, 6.75 g pentaerythritol tetrathioglycolate, and 148 mg azobis(isobutyronitrile). A hard, clear, colorless plate was produced, having a refractive index and Abbe number as given in the Table, infra.
- Example 4 The same procedure as in Example 4 was followed, but with the use of 17.4 g 2,5-bis(methacryloylthio)-3-thiapentane, 13.8 g ethanedithiol dimethacrylate, 6.45 g pentaerythritol tetrathioglycolate, and 148 mg azobis(isobutyronitrile).
- a hard, clear, colorless plate was produced, having a refractive index and Abbe number as given in the Table, infra.
- Example 4 The same procedure as in Example 4 was followed, but with the use of 34.8 g propanedithiol dimethacrylate, 7.4 g glycerin trithioglycolate, and 169 mg azobis(isobutyronitrile). A hard, clear, colorless plate was produced, having a refractive index and Abbe number as given in the Table, infra.
- Example 4 The same procedure as in Example 4 was followed, but with the use of 36.5 g 1,3-propanedithiol dimethacrylate, 9.1 g pentaerythritol tetrakismercaptopropanoate, and 185 mg azobis(isobutyronitrile).
- a hard, clear, colorless plate was produced, having a refractive index and Abbe number as given in the Table, infra.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4234256A DE4234256A1 (de) | 1992-10-10 | 1992-10-10 | Hochlichtbrechende Kunststoffe |
| DE4234256.2 | 1992-10-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5422422A true US5422422A (en) | 1995-06-06 |
Family
ID=6470199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/134,736 Expired - Lifetime US5422422A (en) | 1992-10-10 | 1993-10-12 | High refractive index plastic base on an alkylthiol and an alkylpolythiol ester |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5422422A (de) |
| EP (1) | EP0592934A3 (de) |
| JP (1) | JPH06199964A (de) |
| DE (1) | DE4234256A1 (de) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6342571B1 (en) | 1999-08-20 | 2002-01-29 | Ppg Industries Ohio, Inc. | High refractive index optical resin composition |
| WO2003011925A1 (en) * | 2001-07-25 | 2003-02-13 | Ppg Industries Ohio, Inc. | High refractive index optical resin composition |
| US20050197390A1 (en) * | 2004-02-17 | 2005-09-08 | Chevron Phillips Chemical Company Lp | Thiol ester compositions and processes for making and using same |
| US20060111520A1 (en) * | 2004-02-17 | 2006-05-25 | Chevron Phillips Chemical Company Lp | Polythiorethane compositions and processes for making and using same |
| US20070055033A1 (en) * | 2005-08-16 | 2007-03-08 | Chevron Phillips Chemical Company, Lp | Polymer compositions and processes for making and using same |
| US20070112100A1 (en) * | 2005-08-16 | 2007-05-17 | Chevron Phillips Chemical Company, Lp | Mercaptan-hardened epoxy polymer compositions and processes for making and using same |
| US20080139771A1 (en) * | 2005-01-24 | 2008-06-12 | Roehm Gmbh | Thio(Meth)Acrylates, Mixtures For Producing Transparent Plastics, Transparent Plastics And Method For Their Production And Use |
| US20080214774A1 (en) * | 2007-03-01 | 2008-09-04 | Chevron Phillips Chemical Company, Lp | Thiourethane Compositions and Processes for Making and Using Same |
| US20090124784A1 (en) * | 2007-11-08 | 2009-05-14 | Brown Chad W | Methods and compounds for curing polythiourethane compositions |
| US20090124762A1 (en) * | 2007-11-08 | 2009-05-14 | Brown Chad W | Methods and systems for the selective formation of thiourethane bonds and compounds formed therefrom |
| US20110040355A1 (en) * | 2009-08-12 | 2011-02-17 | Stacy Francis | Phototherapy mask |
| KR101015673B1 (ko) * | 2006-02-22 | 2011-02-22 | 피피지 인더스트리즈 오하이오 인코포레이티드 | 고충격 폴리(우레탄 우레아) 폴리설파이드 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK0779890T3 (da) * | 1995-07-06 | 2001-11-26 | Fraunhofer Ges Forschung | Thiosilaner, fremgangsmåde til fremstilling deraf og anvendelse deraf |
| JPH09152510A (ja) * | 1995-09-25 | 1997-06-10 | Mitsubishi Chem Corp | 低複屈折光学部材及びその製造方法 |
| DE102004011542A1 (de) * | 2004-03-08 | 2005-09-29 | Röhm GmbH & Co. KG | Mischungen zur Herstellung transparenter Kunststoffe, transparente Kunststoffe sowie Verfahren zu deren Herstellung und Verwendung |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0273661A1 (de) * | 1986-12-26 | 1988-07-06 | Nippon Shokubai Kagaku Kogyo Co., Ltd | Ester von Thiolcarboxylsäuren |
| EP0394495A1 (de) * | 1988-10-20 | 1990-10-31 | Sumitomo Seika Chemicals Co., Ltd. | 4,4'-bis(methacryloylthio)diphenylsulfid und vernetzbare zusammensetzung daraus |
| JPH03163120A (ja) * | 1989-11-22 | 1991-07-15 | Showa Denko Kk | 硬化性組成物 |
| JPH04198205A (ja) * | 1990-11-27 | 1992-07-17 | Mitsubishi Petrochem Co Ltd | 高屈折率レンズ用樹脂 |
| US5270439A (en) * | 1988-10-20 | 1993-12-14 | Sumitomo Seika Chemicals Co., Ltd. | Method of producing a curable composition containing 4,4'-bis(methacryloylthio)diphenylsulfide |
| US5294690A (en) * | 1989-02-22 | 1994-03-15 | Toray Industries, Inc. | Thiol methacrylate or acrylate resin |
-
1992
- 1992-10-10 DE DE4234256A patent/DE4234256A1/de not_active Withdrawn
-
1993
- 1993-10-06 EP EP93116145A patent/EP0592934A3/de not_active Withdrawn
- 1993-10-07 JP JP5251739A patent/JPH06199964A/ja active Pending
- 1993-10-12 US US08/134,736 patent/US5422422A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0273661A1 (de) * | 1986-12-26 | 1988-07-06 | Nippon Shokubai Kagaku Kogyo Co., Ltd | Ester von Thiolcarboxylsäuren |
| EP0394495A1 (de) * | 1988-10-20 | 1990-10-31 | Sumitomo Seika Chemicals Co., Ltd. | 4,4'-bis(methacryloylthio)diphenylsulfid und vernetzbare zusammensetzung daraus |
| US5270439A (en) * | 1988-10-20 | 1993-12-14 | Sumitomo Seika Chemicals Co., Ltd. | Method of producing a curable composition containing 4,4'-bis(methacryloylthio)diphenylsulfide |
| US5294690A (en) * | 1989-02-22 | 1994-03-15 | Toray Industries, Inc. | Thiol methacrylate or acrylate resin |
| JPH03163120A (ja) * | 1989-11-22 | 1991-07-15 | Showa Denko Kk | 硬化性組成物 |
| JPH04198205A (ja) * | 1990-11-27 | 1992-07-17 | Mitsubishi Petrochem Co Ltd | 高屈折率レンズ用樹脂 |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6342571B1 (en) | 1999-08-20 | 2002-01-29 | Ppg Industries Ohio, Inc. | High refractive index optical resin composition |
| WO2003011925A1 (en) * | 2001-07-25 | 2003-02-13 | Ppg Industries Ohio, Inc. | High refractive index optical resin composition |
| US7781484B2 (en) | 2004-02-17 | 2010-08-24 | Chevron Phillips Chemical Company Lp | Thiol ester compositions and processes for making and using same |
| US7713326B2 (en) | 2004-02-17 | 2010-05-11 | Agrium Inc. | Controlled release fertilizer material and process for production thereof |
| US20060000252A1 (en) * | 2004-02-17 | 2006-01-05 | Carstens Leslie L | Controlled release fertilizer material and process for production thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP0592934A3 (de) | 1995-02-22 |
| JPH06199964A (ja) | 1994-07-19 |
| EP0592934A2 (de) | 1994-04-20 |
| DE4234256A1 (de) | 1994-04-14 |
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